Alkyl sulfo-alkenyl phenols and salts thereof



Patent Feb. 20, 1951 ,UNlTE ALKYL SULFO-ALKENYL PHENOLS AND SALTSTHEREOF Edward A. Oberrlght, Woodbury, N. 1., or

to Socony-Vacuum Oil Company, a corporation of New York Incorporated,

9 Claims.

This invention has to do with the stabilization of petroleum productsagainst the harmful effects of oxidation and deterioration with use.More specifically, it has to do with the improvement or stabilization ofmineral oil fractions, particularly viscous mineral oils, by the use ofnovel reaction products, or a novel class of reaction products, whichwhen admixed with a mineral oil in minor proportions will prevent ordelay undesirable changes taking place in the oil.

It is well known to those familiar with the art that substantially allof the various fractions obtained from mineral oils and refined fortheir various uses are susceptible to oxidation. This susceptibility ofan oil fraction to oxidation and the manner in which oxidation manifestsitself within the oil varies with the type and degree of refinement towhich the oil has been subjected and with the conditions under which theoil is used or tested. In other words, the deleterious products formedin an oil fraction as a result of oxidation and the degree to which theyare formed depends upon the extent to which the various unstableconstituents, which may act as oxidation catalysts, have been removed byrefining operations, and also upon the conditions of use.

In recent years a great many materials containing one or morecharacterizing chemical elements have been proposed for use asfortifying or stabilizing agents for petroleum products. Ma terialscontaining halogen, metalloid or metals, or combinations of one or moresuch elements, have been credited with improving petroleum products incertain respects. For example, various sulfur-containing materials havebeen proposed for this purpose.

This invention relates to sulfur-containing and sulfurandmetal-containing compounds possessed of the capacity to eii'ectimprovement or mineral oil fractions. More particularly, the presentinvention is predicated upon the discovery of a new and novel class ofoil-soluble compounds represented by the following general formula:

wherein A represents an aromatic nucleus; M is selected from the groupconsisting of hydrogen and metal; R is selectedfrom the group consistingof hydrogen and a hydrocarbon group; a represents the number of R groupsattached to the aromatic nucleus A and is an integer of at least one; Yis selected from the group consisting of a sulfo-alkenyl, aseleno-alkenyl and a telluro-alkenyl group; and b represents the numberof Y groups attached to the aromatic nucleus A and is an integer of atleast one.

The aromatic nucleus A may be monoor polycyclic and is typified byphenyl, naphthyl, anthranyl, etc. As indicated by the foregoing generalformula, and as further described hereinafter, compounds of thisinvention may be derived from a hydroxyaromatic compound having anaromatic nucleus A. Representative hydroxyaromatic compounds which maybe used in preparing the compounds contemplated herein are: phenol,catechol, resorcinol, hydroquinone, pyrogallol, guiacol, aandp-naphthol, anthranol, etc.

As is further indicated by the foregoing general formula, the aromaticnucleus (A) be characterized by one or more hydrocarbon groups (R) ormay only have hydrogen atoms attached to the carbon atoms of saidnucleus. These hydrocarbon groups may be alkyl, aralkyl, alkaryl,cycloalkyl or aryl in nature, all but the latter group, aryl, generallycontributing to increasing the oil solubility of the final compounds. Byway of illustration, R groups include ethyl, amyl, hexyl, keryl (derivedfrom kerosene hydrocarbon fractions), paraflin wax, phenyl, phenylethyl, ethylphenyl, cyclohexyl, and the like. The term paraflin wax asused herein designates petroleum wax, or aliphatic hydrocarbons orhydrocarbon groups of the type which characterize petroleum wax. Theseso-called paraffin wax substituents may be obtained by alkylation of ahydroxy-aromatic compound with a relatively high molecular weightaliphatic hydrocarbon or a mixture of such hydrocarbons (such aspetroleum wax) by any suitable alkylation procedure such, for example,as by a Friedel- Crafts condensation of a chlorinated petroleum wax withphenol to form paraffin wax-phenol.

The compounds represented above by the general formula are characterizedby the presence therein of a sulfa-, selenoor telluroalkenyl group,which group is formed by reaction of sulfur, selenium or tellurium,respectively, with an olefinic( C=C group of an alkenyl group.Preferaby, one to three such groups are present in the compounds of thisinvention. Typical alkenyl groups are propenyl, butenyl, hexenyl,crotonyl, etc.

As indicated herelnabove, the compounds may also contain metal, in whichcase the compounds so characterized are metal phenates. Any metal may beused the oxide or hydroxide of which auaesa (in alcoholic solution, ifnecessary) can be reacted with a hydroxyaromatic compound. or a salt ofwhich can be reacted in alcohol solution with the sodium salt of ahydroxyaromatic compound. For example, the said sodium salt can bereacted with an alcohol solution of a salt of the desired metal, such asstannous chloride, lead acetate, thorium nitrate, titaniumtetrachloride, etc. Among the metals contemplated forthis purpose are:copper, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium,mercury, germanium, tin, lead, vanadium, chromium,

manganese, iron, cobalt, nickel, ruthenium, palladium, platinum,aluminum, antimony, arsenic, bismuth, cerium, columbium, gallium, gold,iridium, indium, molybdenum, osmium, rubidium, selenium, tantalum,tellurium, thorium, titanium, tungsten, uranium and zirconium.Preference is given to metals of the alkaline earth group. particularlyto barium.

In addition to the aforesaid R, Y, OH and OM characterizing groups, thearomatic nucleus (A) may also have attached thereto one or more suchcharacterizing groups as amino, nitro, carboxy, carbonyl, hydroxylamineand the like. It will be apparent, of course, that the number of suchgroups which may be attached to the aromatic nucleus will be dependentupon the number of nuclear carbon atoms not having attached thereto, R,Y, OH or OM groups.

The compounds of this invention may be prepared by any one of severalprocedures known to the chemical art. They may be prepared by reactingsulfur, for example, with an alkenyl phenyl ether, whereupon the alkenylgroup is sulfurized and the sulfurized alkenyl group so formedrearranges to the nucleus, thus forming a sulfo-alkenyl phenol.Rearrangement is demonstrated by the absence of hydrogen sulfidedevelopment during the reaction. A preferred procedure involves reactingabout one gram atom of sulfur with one molar proportion of an alkenylphenyl ether at 150-250" C. for such time as to obtain a productnon-corrosive to a' copper strip when such a strip is placed in a oneper cent blend of said product in oil, and the oil blend is Anothermethod of preparation involves re arrangement of the alkenyl group of analkenyl aryl ether to the aryl nucleus, followed by reaction of therearranged compound, namely, an alkenyl-substituted aryl hydroxyaromaticcompound, with sulfur,'selenium or tellurium. This rearrangement may beaffected by heating the ether at a temperature slightly in excess of itsboiling point, alone or in the presence of diethylaniline; or heatingthe said ether at reflux over a re atively lon period of time with a diute sulfuric acid-acetic acid mixture. Other typical methods ofpreparation include sulfurizing, for

example, alkenyl hydroxyaromatic compounds formed by: reacting anunsaturated aldehyde with a phenol; reacting a phenol with 2-methylcyclohexanone in the presence of hydrochloric acid; chlorination of analkyl group of an alkyl phenol followed by dehydrohalogenation; etc.

EIKAIHPLE I Diamyl sulfa-methallyl phenol Sodium diamyl phenate wasprepared by grad- -ually adding small pieces of sodium (total quantity11.5 grams; 0.5 mol) to a mixture of diamyl phenol (117 grams; 0.5 mol)and butyl alcohol. Methallyl chloride (70 grams, 50% excess; 0.75 mol)was then added dropwise to the sodium diamyl phenate at 100 0., and theresulting mixture was refluxed at 110-120 C. for eleven hours.Thereafter, the mixture was washed with water to remove sodium chlorideformed in the reaction of methallyl chloride and the said phenate. Butylalcohol and any unreacted methallyl chloride were removed from thewater-washed mixture by distilling the latter to a maximum temperature.of 175 C. at 15 mm. pressure. The product, predominantly diamylphenylmethallylether, had a hydroxyl value of 44 (theoretical=0) and an iodinevalue of 8,9 (theoretical=88). The hydroxyl value is due to unreacteddiamyl phenol or to rearrangement of the methallyl group to the nucleus.

Fifty grams of diamylphenyl methallylether,

, prepared as described above, was heated to 175 C. and 4 grams ofsulfur per cent of theoretical) were slowly added thereto. The reactionmixture so obtained was heated for two hours at 175 C. and was filteredthrough paper. The product, diamyl sulfomethallyl phenol, contained 8.6per cent sulfur and had a hydroxyl value of 163; correspondingtheoretical values are 10 per cent and 175.

EXAMPLE II Barium phenate of diamyl sulfa-methallyl phenol A mixture of12 grams of diamyl sulfo-methallyl phenol (prepared as indicated inExample I above), 2.4 grams of barium (59 grams of 4 per cent bariumbutylate solution) and 24 grams of mineral oil was refluxed for twohours. Butyl alcohol was removed from the reaction mixture by distillingthe latter to a maximum temperature of 150 C. at 15 mm. pressure, andthe alcohol-free product was filtered through a filter aid (Hi-Floclay). The product, barium phenate of diamyl sulfo-methallyl phenol, inthe oil blend in which it was made analyzed 3.8 per cent barium and 2.5per cent sulfur. On a concentrate basis, this corresponds to 11.2 percent bari and 7.5 per cent sulfur. I

EXAMPLE III Paraffin wax-phenyl sulfa-methallyl phenol Sodium paraffinwax phenate was made by gradually adding 3.7 grams of sodium metal to100 grams of paraflin wax phenol (2-12) in butanol, the latter acting asa solvent. The said phenate was heated to C. and 28.8 grams of methallylchloride were slowly added thereto over a period of 15 minutes. Thereaction mixture so formed was heated at 90 C. for 6 hours, cooled,water washed, and distilled to a maximum temperature of 175 C. at 15 mm.pressure, whereupon paraflin wax-phenyl methallyl ether (2-12) wasobtained. The paraflln wax-phenol (2-12) used in this example wasprepared by the usual Friedel-Crafts procedure outlined in Patent No.2,853,491, issued July 11, 1944.

Ninety-five grams of paraflin wax-phenyl methallyl ether (2-12),prepared as described above, was heated to 185 C. and 2.8 grams ofsulfur were added thereto during a 10 minute period. The resultingreaction mixture was heated at 185 C. for 5 hours. Thereafter, themixture was cooled, diluted with benzol and filtered. The filtrate thusobtained was distilled at a maximum temperature of 150 C. at mm.pressure whereupon benzol was removed. The product is panallinwax-phenyl sulfo-methallyl phenol (242),

EXAMPLE IV Barium oxide in methyl alcohol, 8.3 grams of barium as bariumoxide, was slowly added to 95 grams of paraffln wax-phenylsulfo-methallyl phenol (2-12), prepared as described in Example 111above, in 190 grams of mineral oil at 75 C. Methyl alcohol was distilledfrom the reaction mixtur obtained during the addition and completeremoval thereof was insured by raising the temperature of the reactionmixture to 150 C. The reaction mixture so obtained was cooled and benzolwas added thereto. The benzol mixture was then filtered through Hi-Floand benzol was removed from the filtrate by distilling the latter to amaximum temperature of 175 C. at 15 mm. pressure. The product, bariumphenate of paraffin wax-pheny1 sulfo-methallyl phenol (2-12), contained4.0 per cent barium and 1.9 per cent sulfur on a concentrate basis.

As indicated hereinabove, the compounds contemplated by this inventionand illustrated by the foregoing examples, when added to mineral oils inminor proportions have been found to improve these oils in severalimportant respects. This phenomenon is de onstrated in the followingtables, which contain results of the various tests conducted todetermine the effectiveness of these compounds as addition agents forlubricating oils. The per cent of compound added to the oil in eachtable is the per cent of compound per se and does not include the oil inwhich the compound was made.

CORROSION INHIBITION Motor oils, especially those refined by certainsolvent-extraction methods, tend to oxidize when submitted to hightemperatures and to form products that are corrosive to metal bearings.This corrosive action may be quite severe with certain bearings, such asthose having the corrosion-susceptibility of cadmium-silver alloys; andmay cause their failure within a comparatively short time. The followingtest was used to determine the corrosive action of motor oil on anautomobile connecting rod bearing.

The oil used consisted of Pennsylvania neutral and residuum stocksseparately refined by means of chlorex and then blended to give an S. A.E. motor oil with a specific gravity of 0.872, a flash point of 435 F.,and a Saybolt Universal viscosity of 318 seconds at 100 F. The oil wastested by adding a section of a bearing containing a cadmium-silveralloy surface, weighing about 6 grams, and heating it to 175 C. for 22 8hours while a stream of air was bubbled against the surface of thebearing. The loss in weight of the bearing during this treatmentmeasures the amount of corrosion that has taken place. A sample of the011 containing a stabilizing agent was run at the same time as a sampleof the straight oil, and the loss in weight of the bearing section inthe inhibited oil can thus be compared directly with the loss of thesection in the uninhibited oil. The results obtained in this t test areset forth in Table I below:

ACCELERA'I'ED CORROSION TEST This test is used to determine thecorrosive nature of lubricating oils under simulated operatingconditions. The apparatus used consists of a circulating arrangementwhereby oil at 325 F., under a pressure of 10 pounds per square inch, issprayed against a standard cadmium-nickel bearing for a period of 5hours. The amount of oil under constant circulation in the system is1500 cc. In passing through the system, the oil comes in contact withcast iron, steel, stainless steel, copper, and the aforesaidcadmium-nickel bearing, and is also exposed to aeration. The oil used inthis test contains a small amount of an accelerator, namely, ironnaphthenate (commercially designated as Nuodex, 6 per cent F6203) whichgreatly increases the rate of oxidation of the oil. The degree ofoxidation suffered by the oil is shown by the development of aciditytherein as measured by the neutralization number (N. N.), the loss inweight in grams of the cadmium-nickel bearing and the percentage ofviscosity increase.

The specific base oil used in this test was a solvent refined oil havinga Saybolt Universal viscosity (S. U. V.) of 65 seconds at 210 F. andcontaining 0.17 per cent of Nuodex; and the oil blends contained smallamounts of typical compounds in the base oil. The results of these testsare set forth in Table II shown below:

Table II Cone. Percent Loss in Stabilizing agent (Weight N. N. Viscositygrams of Per Cent) lncr. Cd-Ni bearing None 8 107 l. 69 Diamylsulfo-methallyl 5 p en 2.0 5.2 50 0.0? Barium phenate oi diaml J ylsulfo-allyl phenol 1.0 i 8 ll 0. 822

LAUSON ENGINE TEST To further demonstrate the eifectiveness of thecompounds contemplated herein as petroeum oil stabilizers, blank oilsand blends of said oils and typical compounds were subjected to LausonEngine Tests. In this test, a single cylinder Lauson engine was run withan oil temperature of 290 F. and a jacket temperature of 212 F. The oilused was an S. A. E. motor oil, solvent refined. The neutralizationnumber (N. N.) and viscosity, in cent! stokes at 210 1''. of the 011 andoil blend, were determined after 36 hours. The results are shown belowin Table 111.

Table III bilizing Agent i ght N N K V Sta e Cent) 210 F.

id-Aourtm None 4.8 50.4 Diamyl sulio-methaliyl phenol. 1.0 2. 9 47. 8None 6.8 63.7 Barium henate of diamyl sulfomet yl phenol 0.5 1 7 46.4 IMaurice! Nona h I 1 sun. 7.0 51.3 Barium enate my 0- allyl ph noi 1. 02. 7 48, 9 None 6.2 52.6 Barium phanate of paramu wax suliomethallylphenoL; 1.0 4 6 51.

It will be apparent from the foregoing representative test data that thecompounds of this invention are eflective oil stabilizing agents.

The amount of stabilizing agent used varies with the mineral oilfraction with which it is blended and with the properties desired in thefinal oil composition. These condensation products may be added tomineral oil in amounts of from about 0.01 per cent to about 5.0 percent, but amounts of the order of 1.0 generally provide satisfactoryimprovement.

It is to be understood that although I have described certain preferredcompounds and procedures which may be followed inthe preparation of thesame, such compounds and procedures are illustrative only. Accordingly,this invention is not to be considered limited thereto or thereby, butis to be broadly construed in the light of the language of the appendedclaims.

This application is a division of my copending application, Serial No.624,097, filed October 23, 1945.

I claim:

1. As a new composition of matter, a compound represented by the generalformula:

wherein A represents a carbocyclic aromatic nucleus; M is selected fromthe group consisting of hydrogen and metal; R is selected from the groupconsisting of a replaceable nuclear hydrogen atom and a hydrocarbongroup substituted for one of said replaceable nuclear hydrogen atoms; arepresents the number of R groups attached to the aromatic nucleus A andis an integer from 1 to 4; Y is an alkenyl group, the olefinic bond ofwhich has been satisfied by the addition thereto of an atom selectedfrom the group consisting of'sulfur, selenium and tellurium; and 1)represents the number of Y groups attached to the aromatic nucleus A andis an integer from 1 to 3.

2. As a new composition of matter, a compound represented by the generalformula:

wherein A represents a carbocyclic aromatic nucleus, M is selected fromthe group consisting of hydrogen and metal; R is selected from the group:onsisting of a replaceable nuclear hydrogen atom and a hydrocarbongroup substituted for me of said replaceable nuclear hydrogen atoms;

a represents the number of R groups attached to the aromatic nucleus Aand is an integer from 1 to 4; Y represents an alkenyl group, theolefinic bond of which has been satisfied by the addition of a sulfuratom thereto; and b represents the number of Y groups attached to thearomatic nucleus A and is an integer from 1 to 3.

3. As a new composition of matter, a compound represented by the generalformula:

wherein A represents a carbocyclic aromatic nucleus; M is metal, R isselected from the group consisting of a replaceable nuclear hydrogenatom and a hydrocarbon group substituted for one of said replaceablenuclear hydrogen atoms; a represents the number of R groups attached tothe aromatic nucleus A and is an integer from 1 to 4; Y represents analkenyl group, the olefinic bond of which has been satisfied by theaddition of a sulfur atom thereto; and b represents the number of Ygroups attached to the aromatic nucleus A and is an integer from 1 to 3.

4. As a new composition of matter, a compound represented by the generalformula:

wherein A represents a carbocyclic aromatic nucleus; R is selected fromthe group consisting of a replaceable nuclear hydrogen atom and ahydrocarbon group; a represents the number of R groups attached to thearomatic nucleus A and is an integer from 1 to 4; Y represents analkenyl group, the oleflnic bond of which has been satisfied by theaddition of a sulfur atom thereto and b represents the number of Ygroups attached to the aromatic nucleus A and is an integer from 1 to 3.

5. As a new composition of matter, diamyl methallyl phenol, the oleflnicbond of the methallyl radical having been satisfied by the addition of asulfur atom thereto.

6. As a new composition of matter, barium phenate of diamyl allylphenol, the olefinic bond of the allyl radical having been satisfied bythe addition of a sulfur atom thereto.

7. As a new composition of matter, a compound of the general formula OMR.-iL-Ya 0M R.-.L-CH:C CH1 wherein A represents a carbocyclic aromaticnucleus; M is barium; R is a hydrocarbon group;

a represents the number of R groups attached to the aromatic nucleus Aand is an integer from 1 to 4.

9. As a new composition of matter, a barium phenate of a parafflnwax-alkylated methallyl phenol, the olefinlc bond of the methallyl grouphaving been satisfied by the addition of a sulfur atom thereto and theparaffin wax substituent being attached to the phenol nucleus andcorresponding to an alkyl radical of a paraflin wax melting at about 120E, which wax was first chlorinated to a chlorine content of from about12 to about 16 per cent by weight of chlorine and then used as thealkylating agent in forming said paraffin wax-alkylated methallylphenol.

EDWARD A. OBERRIGH'I'.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,185,660 Coltof Jan. 2, 19402,225,573 Tendeloo Dec. 17, 1940 2,260,953 Rebold Oct. 28, 19412,361,051 Patterson Oct. 24, 1944 2,409,687 Rogers Oct. 22, 19462,422,275 Winning June 17, 1947 2,422,276 Mikeska June 17', 1947Certificate of Correction Patent No. 2,542,832 February 20, 1951 EDWARDA. OBERRIGHT It is hereby certified that error appears in the printedspecification of the above numbered patent requiring correction asfollows:

Column 1, line 40, for the words improvement or read improvement of;column 2, line 18, for (A) be read (A) may be; column 8, line 34, forgroup read group substituted for one of satcl replaceable nuclearhydrogen atoms; and that the said Letters Patent should be read ascorrected above, so that the same may conform to the record of the casein the Patent Oflice.

Signed and. sealed this 28th day of August, A. D. 1951.

[snAL] THOMAS F. MURPHY,

Assistant Commissioner of Patents.

Certificate of Correction Patent No. 2,542,832 February 20, 1951 EDWARDA. OBERRIGHT It is hereby certified that error appears in the printedspecification of the above numbered patent requiring correctlon asfollows:

Column 1, line 40, for the Words improvement or read improoement of;column 2, line 18, for (A) be read (A) may be; column 8, line 34, forgroup read group substituted for one of said replaceable nuclearhydrogen atoms;

and that the said Letters Patent should be read as corrected above, sothat the same may conform to the record of the case in the PatentOflice.

Signed and sealed this 28th day of August, A. D. 1951.

[SEAL] THOMAS F. MURPHY,

Assistant C'ommz'ssz'oner of Patents.

1. AS A NEW COMPOSITION OF MATTER, A COMPOUND REPRESENTED BY THE GENERALFORMULA: